CA1328528C - Thermosetting resin composition, printed circuit board using the resin composition and process for producing printed circuit board - Google Patents
Thermosetting resin composition, printed circuit board using the resin composition and process for producing printed circuit boardInfo
- Publication number
- CA1328528C CA1328528C CA000614073A CA614073A CA1328528C CA 1328528 C CA1328528 C CA 1328528C CA 000614073 A CA000614073 A CA 000614073A CA 614073 A CA614073 A CA 614073A CA 1328528 C CA1328528 C CA 1328528C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
- C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/901—Printed circuit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31547—Of polyisocyanurate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Engineering & Computer Science (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is a fluorine atom, a bromine atom and a chlorine atom, R2 is an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is any one of a polymerization initiator residue, a polymerization-terminating agent residue, H and
A thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is a fluorine atom, a bromine atom and a chlorine atom, R2 is an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is any one of a polymerization initiator residue, a polymerization-terminating agent residue, H and
Description
This invention relates to a thermosetting resin composition and its uses, and particularly to a - thermosetting resin composition for a printed circuit board having a good flame retardness and a printed circuit board using the resin composition.
Heretofore, phenol resin, epoxy resin, polyimide resin, etc. have been used as resin materials for multi-layered printed circuit boards to be used in electronic computers, etc. Recent large-scale electronic computers require a high speed computation and thus strict characteristics are required for the multi-layered printed circuit boards for this purpose and development of new materials for the multi-layered printed circuit boards is now in progress.
Generally, the computing speed of an electronic computer largely depends on the signal transmission speed of the circuit on a multi-layered printed circuit board used in the electronic computer.
The signal transmission speed of the circuit also depends on the dielectric constant of the insulating ` layer. The lower the dielectric constant, the higher the signal transmission speed. Thus, the computing speed of an electronic computer can be improved by making a printed circuit board from materials of low 1 dielectric constant.
Polytetrafluoroethylene (PTFE), polybutadiene, -etc. are known as materials of low dielectric constant.
Furthermore, cyanate compounds (US Patent No.
4,559,3999) or isocyanate compounds (US Patent No.
4,353,7691) having a structure of low polarization based on an aromatic group or alicylic group or a combination thereof on the main chain are also known as materials of low dielectric constant.
PTFE belongs to a thermoplastic resin and has problems such as poor dimensional stability and through-hole reliability, when used in multi-layered printed circuit boards. Still furthermore, no appropriate solvent is available for PTFE and thus the lamination ; 15 bonding has been relied only on a heat fusion pressing.
Owing to a high melting temperature such as 250C to 350C, PTFE has a poor workability and problems in the handling, as compared with the conventional epoxy resin, etc.
As to the polybutadiene, on the other hand, resin materials based on a combination of 1,2-polybutadiene having double bonds on the side chains with a cross-linking type flame retardant based on bifunctional monomers have been developed [Japanese i 25 Patent Application Kokai ~Laid-open) No. 55-126~51].
When a lower molecular weight polymer is used in view of the impregnation property toward fibrous substrate materials, the tackiness of the resulting prepreg is so _ ~ _ .. . , ~ , .
. ' - , ` -l high that it is difficult to cut~ ve the prepreg and also an adverse effect is given on the lamination-bonding workability. When a higher molecular weight polymer is used in view of a low tackiness or tackfree-ness of a prepreg, the impregnation property towardfibrous substrate materials is deteriorated due to the higher varnish viscosity and it is not easy to prepare a prepreg. That is, the resulting printed circuit boards have no satisfactory qualities. Furthermore, the curing reaction is a cross-linking reaction based on radical polymerization and thus the reaction rate is so high that its control is not easy. Still furthermore, ~ polybutadiene is liable to form cracks, when molded, ; because of a high curing shrinkage and has low mechanical strength and heat resistance and a low adhesion to copper foils that form circuits.
~ he cyanate compounds or isocyanate compounds are trimerized in the presence of a catalyst to form cured products of high cross-linking density. The cured products have a low dielectric constant and good dimensional stability and heat resistance, but has no - satisfactory flame retardness as an important character-istic of printed circuit boards.
In order to improve the foregoing dis-advantages, Japanese Patent Application Kokai tLaid-open) No. 61-243844 proposes a thermosetting resin composition comprising a prepolymer of poly(p-hydroxystyrene) derivative and 1,2-polybutadiene or its ., ~B
.
,`~ . .
. ~ , 1 32~528 derivative, a laminated board using the resin composition, and a process for producing the laminated board, and Japanese Patent Application Kokai (Laid-open) NO. 62-192406 proposes a flame-retarding resin compo-~ 5 sition comprising a prepolymer of poly(p-hydroxystyrene) derivative as an essential component, and a prepreg and a laminated board using the resin composition, but the laminated boards made from these resin compositions still have problems in the moisture absorption, : 10 chronological change and mechanical characteristics at : an elevated temperature.
SUMMARY OF THE INVENTION
An object of the present invention is to ; provide a flame-retardant, thermosetting resin composition, a printed circuit board using the resin composition and a process for producing the printed circuit board, free from the foregoing disadvantages of the prior art.
According to the first aspect of the present invention, there is provided a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
. A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-~ - 4 -', ~
.
~ 1 328528 ative represented by the following general formula (II):
B - - C~2-C~ ~ B
~ ~ (II) ~ OR2 Jn wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and ! CH=CH-(X)m , m is an integer of 1 to 4 and n is an integer of 5 to 100: wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
According to the second aspect of the present invention there is provided a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - Rl - A (I) , wherein R1 is an aromatic group, an alicyclic group or ' 20 a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-., .
, - 5 -`` iD
!
, --` 1 328528 ative represented by the following general formula (II):
B - r CH2-CH r B
X)m ~ (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, Rz is selected from an alkenyl . 5 group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of 1 to 4 and n is an integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group: wherein the mixing ratio of the Compound (I) to the Compound (II) in . the resin composition is in the range of 20:80 to 80:20 by weight.
. 15 According to the third aspect of the present invention there is provided a curable material which aomprises a woven fabric or non-woven fabric of inorganic fibers or organic ~ibers, impregnated with a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
, .
~B
:
"
, .
.
. . .
.. .. . . ~ .
... . . . . .
., . ~
. .
. .
. . . . . . .
~ - . .
1 32852~
A - R1 ~ A (I) wherein R1 is selected from an aromatic group, an alicyclic group or a mixed group thereof and A is selected from a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
X)m (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an integer of 5 to lO0: wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin ; composition is in the range o~ 20:80 to 80:20 by weight;
or a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula ~
A - R1 ~ A (I) 1'~
, ~ . . . . .
.~ . : - . :
"' ~' ~ ~ ' ' . ' ' : ~ ..
- 1 32852~
- wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
, l ~ ~x)mJ (II~
: OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl : group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group: wherein the mixing ratio of the Compound ~I) to the Compound ~II) in the resin composition is in the range of 20:80 to 80:20 by weight.
According to the fourth aspect of the present invention, there is provided a printed aircuit board, which comprises a conductor of a metallic foil and an ; insulating layer made of a fibrous substrate material . - 8 -I ~S
: . -.. ~ . , impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
~ (X)m~ (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 ; to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an integer of 5 to lO0; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
According to the fifth aspect of the present , j.'~' ~, , -. , ; .
invention there is provided a printed circuit board, which comprises a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - Rl - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(X)m (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, 3 is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-~ (X)m , m is an integer of l to 4 and n is an B
'' ' ~ . ', `~ :
integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 ; 5 by weight.
According to the sixth aspect of the present invention, there is provided a multi-layered, printed circuit board, which comprises a lamination of a plurality of printed circuit boards each comprising a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) . wherein R1 is an aromatic group, an alicyclic group or amixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula : (II):
, B - - CH2-fH - B
:l ~ (X)m, (II) OR2 n wherein X is selected from a fluorine atom, a bromine ~, ', - 11 -~ .
,, .
. . , , ~ ~ ~
atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and ,CH=CH- !
(X)m , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight:
10 or printed circuit boards each comprising a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an 15 isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an ; 20 isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II) : B - - CH2-CH I B
(X~m (II) OR2 n !~
.
, .
'' -wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization S initiator residue, a polymerization-terminating agent residue, H and CH=CH-X)m , m is an integer of l to 4 and n is an integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
: According to the seventh aspect of the presentinvention there is provided a process for producing a printed circuit board, which comprises:
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - Rl - A ~I) wherein R~ is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
IB, :. . .. .
. . ~
~` 1 32~528 B - - CH2-~ - B
~x)m J (II) OR2 n :
wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, Rz is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent ~ residue, H and 2 CH=CH-` ~ (X)m , m is an integer of l to 4 and n is an integer of 5 to lO0, thereby forming a prepolymer;
wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight;
a step of dissolving the prepolymer in a ` solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby ; preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
According to the eighth aspect of the present :j ~
~.
.:
. . . - , ~ , .
'............ , : ~ .
: .
;. ...
` 1 328528 invention there is provided a process for producing a printed circuit board, which comprises:
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
, ~
B--CH2-C~I ~ B
~(X)m (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an Rz integer of 5 to 100 and a compound having at least one N-substituted unsaturated imido group, wherein the B
.
. . , ~ ., . . ~ ., ... , .. . . .. " .. ,. .. ` .
..
.. .. ~,, i, `. ~.
"` 1 328528 mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight, thereby forming a prepolymer;
a step of dissolving the prepolymer in a solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby - preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
The present inventors have found that a resin composition having a good flame retardness, a low moisture absorption and a high mechanical strength at an elevated temperature can be obtained without impairing the dielectric constant by combining at least one of cyanate compounds and isocyanate compounds represented by the foregoing general formula (I) with a cross-linking type, flame retardant represented general formula (II) and have established the present invention.
In the present invention, the aromatic group and the alicyclic group represent by Rl in the general formula (I) include:
( C ) m ( C ) ~( ~
etc.
' ' j ~
, .
-- 1 wherein C is -H, -CH3, -CH2CH3; D is -OCN and -NCO;
Il l l 11 E is -, -CH2-, -O-, -S-, -C- , -C- , -f- or -S- ;
: m is an integer of 1 to 4 and n is O and an integer of 1 ~: to 3, and the mixed group thereof is a group having at least a few of the foregoing aromatic and alicyclic groups in the skeleton structure and can have a plurality of the same aromatic or alicyclic groups as linked in succession in the skeleton structure.
Specific examples of the compounds represented by the general formula (I) include 2,2-bis(4,4'-di-cyanatophenyl)propane, 2,2-bis(4,4'-diisocyanatophenyl)-propane, tetramethylxylenedicyanate, tetramethylxylene-diisocyanate, diphenylmethane dicyanate, diphenyl-methanediisocyanate, cyanates and isocyanates whose R1 is 4,4'-dihydroxydiphenyloxide, resorcinol, 4,4'-thio-diphenol, 3,3',5,5'-tetrabromobisphenol-A, 2,2',6,~'-tetrabromobisphenol-A, 3-phenylbisphenol-A, 4,4'-di-hydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,2',4,4'-: tetrahydroxybiphenylmethane, 2,2',6,6'-tetramethyl-3,3',5,5'-tetrabromobisphenol-A, 5,5'-dimethoxybis-phenol-A, bisphenol of dicyclopentadiene, or bisphenol of tricyclopentadiene, polycyanates and polyisocyanates of phenol-formaldehyde condensates, polycyanates and polyisocyanates of phenoldicyclopentadiene condensates, polycyanates and polyisocyanates of 2,2',4,4'-tetra-hydroxy diphenylmethane, etc. and can be used alone or .~
.~
:-.
- 1 32~528 1 in combination of at least two thereof.
Specific examples of the compound represented by the general formula (II) include poly(p-vinylbromo-phenylallylether), poly (p-vinyl-bromophenylisopropenyl-ether), poly(p-vinylbromophenyl-l,l'-dimethylbutenyl-ether), poly(p-vinylbromophenylmethacrylate), poly(p-inylbromophenylallylether), etc, where n of the compound (II) can be an integer of 5 to 100, and depends on the species and molecular weight of the compound ~I) to be used together and also on a mixing ratio of the compound ~I) to the compound ~II). When n exceeds 100, the viscosity of the resin composition will be higher and the impregnation toward the substrate material will be deteriorated, resulting in occurrence of voids at the lamination-bonding. When n is below 5, on the other hand, the preservation stability of the resin composi-tion will be deteriorated and the flowability of the resin composition will be higher, resulting in the resin loss at the lamination-bonding.
The mixing ratio of the compound (I) to the compound ~II) in the resin composition is in a range of 20:80 to 80:20 by weight. When the compound (I) is contained in a mixing ratio of more than 80, no satisfactory flame retardness can be obtained, whereas the mixing ratio of the compound (II) is more than 80, the feature of materials of low dielectric constant cannot be fully obtained.
A compound having at least one of N-;, .. . .
1 substituted, unsaturated imido groups can be added to the resin composition comprising the compound (I) and the compound (II) as a cross-linking promoter, and in-cludes, for example, bismaleimides such as N-substituted phenylmaleimide, phenylcitraconimide, phenylitacon-imide, phenylnadic imide (phenylmethylendomethylene-tetrahydrophthalimide), N,N'-p-phenylenebismaleimide, N,N'-p-phenylenebismethylendomethylenetetraphthalimide, N,N'-p-phenylenebiscitraconimide, N,N'-p-phenylenebis-itaconimide, N,N'-m-xylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-(methylene-di-p-phenylene)bismaleimide, N,N'-4,4'-diphenylthioetherbismaleimide, N,N'-4,4'-diphenylether-bismaleimide, N,N'-methylenebis(3-chloro-p-phenylene)-bismaleimide, N,N'-(sulfonyl-di-p-phenylene)bismale-imide, N,N'-4,4'-diphenylcyclohexanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis~4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimido-2-trifluoromethylphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, etc., and multi-valent maleimides obtained by reaction of a condensate of aniline and aldehyde with maleic anhydride and repre-sented by the following general formula (III), etc:
CH2- ~ CH2- ~ (III) ~N~ ~N~ ,N\
of clo of clo of clo CH = CH ~ CH = CH , P CH = CH
' -- .
.
:'' ' , ' ', i, -: .
1 32852~
1 where p is an integer of 1 to 10.
The present process for producing a laminated board will be described below.
A resin composition composed of the compound (I) and the compound (II) is dissolved in an organic solvent in a mixing ratio in the aforementioned range to prepare a varnish having a resin content of 20 to 80% by weight. To promote the dissolution, heating can be conducted. As the organic solvent, toluene, xylene, methylethylketone, methylisobutylketone, methanol, ethanol, 3-methoxypropanol, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trichloroethylene, etc., or those which can uniformly dissolve the compounds (I) and (II) can be used alone or in combination.
A trimerization catalyst for the cyanate group or the isocyanate group and a radical polymerization initiator is then added to the thus prepared varnish to make an impregnation varnish. As the trimerization catalyst, metal salts such as cobalt naphthenate, cobalt octenoate, zinc octenoate, potassium acetate, sodium acetate, sodium cyanide, sodium cyanate, sodium ; isocyanate, sodium boride, etc.; sodium methoxide;
sodium hydroxide; organic base such as pyridin; tertiary amines such as triethylamine, etc.; Lewis acids such as aluminum chloride, bromine trifluoride, ferric chloride, titanium chloride, zinc chloride, etc. can be used. As ' the radical polymerization initiator, benzoyl peroxide, :, ',"
..
1 dicumyl peroxide, methylethylketone peroxide, t-butyl peroxylaurate, di-t-butyl peroxyphthalate, dibenzyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, etc. can be used. 0.1 to 10 parts by weight of these trimerization catalyst and radical polymerization initiator is used per 100 parts by weight of the resin composition.
Then, a fibrous substrate material is impreg-nated and coated with the thus prepared impregnation varnish and dried at room temperature to 170C to obtain a prepreg free from the tackiness. The drying tempera-ture depends on the species of the solvent and radical polymerization initiator used.
Then, a desired number of the thus obtained prepregs is laid upon one another and cured with heating at 120C to 250C under a pressure of 1 to 100 kg f/cm2 to obtain a laminated board.
As the fibrous substrate material, those usually used as laminated board materials can be used in the present invention. Woven fabrics or non-woven fabrics of inorganic fibrous substrate materials such as glass fibers, for example, E glass fibers, C glass fibers, A glass fibers, S glass fibers, D glass fibers, YM-31-A glass fibers containing SiO2, A12O3, etc. as main components, and A glass fibers made of ~uartz, etc.
or woven fabrics or non-woven fabrics of organic fibers such as aramid fibers containing polymer compounds having as aromatic polyamide-imide skeleton can be used ;
- : . . . ' ~` 1 328528 1 in the present invention.
In the present invention, an inorganic filler such as silica powder, etc. or an organic filler such as perfluoroethylene powder, polyimide powder, polyamide powder, etc. can be added to the resin composition, and it is particularly important in attaining the effect of the present invention to use a filler having a di-electric constant of not more than 3.3.
That the present thermosetting resin composi-tion can produce a laminated board of low dielectricconstant and a good flame retardness is not only due to the fact that the cyanate compound or the isocyanate compound (I) itself has a low dielectric constant, but also due to the fact that the cross-linking type, polymeric flame retardant (II) is a material of un-expectedly low dielectric constant and further that the flame retardness and electric characteristics are not deteriorated even by copolymerization of the cross-linking type, polymeric flame retardant ~II) with the cyanate or isocyanate compound (I).
The present invention will be described in detail below, referring to Examples and the accompanying drawin~s.
q BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows process steps for preparing a board laminated with copper foils at both outer sides, as viewed in cross-section.
' ~;' . ~
. .......................................... . .
-`- 1 328528 l Fig. 2 shows a process step for preparing an inner layer circuit board as viewed in cross-section.
Fig. 3 shows a process step for preparing a multi-layered printed circuit board.
In Figs. 1 to 3, numerals 1 is a varnish prepared from the present resin composition; 1' is uncured resin; 2 a glass cloth; 3 a prepreg; 4 a copper foil; 5 a hot plate; 6 a copper-laminated board; 7_a cured resin; 8,8' and 8" inner layer circuit boards; 9 a multi-layered, printed circuit board; 10 an inner layer printed circuit; 11 an outer layer printed circuit; and l2 a through hole.
PREFERRED EMBODIMENTS OF THE INVENTION
Example 1 XU-71787 (trademark of a cyanate compound prepared by Dow Chemical Company, USA) represented by the general formula (I; and poly-(p-vinylbromophenyl-methacrylate represented by the general formula ~II) [average molecular weight: 6,600; m is about 2 and n is about 20 in the general formula (II)] as a flame retard-ant were mixed in a mixing ratio of 1:1 by weight and the resulting resin compositlon was dissolved in N,N-dimethylformamide as a solvent with heating at 60C for 30 minutes to prepare a varnish having a solid content of 50 % by weight. After cooling, 0.5 parts by weight of 2,5-di(t-butylperoxy) hexine-3(made by Nihon Yushi K.K., Japan) as a radical polymerization initiator and ., .
. ~ . . .
. , ~ :
,, . : .
1 ~28528 1 0.5 parts by weight of cobalt naphthenate as a tri-merization catalyst for the cyanate compound were added to the varnish on the basis of 100 parts by weight of the resin composition to prepare an impregnation s varnish.
Glass cloth (250 mm square; thickness: 0.05 mm; E glass made by Nitto Boseki K.K., Japan) was impregnated and coated with the thus prepared varnish and dried in air at 150C for 10 minutes to prepare a prepreg, 250 mm square, (resin content: 40 - 70 % by weight).
Then, 20 sheets of the thus prepared prepregs were laid one upon another and pressed between a pair of hot plats under a pressure of 30 kg f/cm2 at first at 130C for 40 minuts, then at 170C for one hour, and lastly at 200C for one hour with heating to cure the resin to obtain a laminated board.
Separately, the impregnation varnish was applied to a polyethylene terephthalate sheet and dried at 150C for 10 minutes to obtain a powdery resin ~ composition. The thus obtained resin composition was ;~ press-molded into a plate form, 15 cm x 10 cm x 2 mm thick, and cured under the same conditions as used for the preparation of the prepreg as above, to form a resin plate.
:.
Example 2 A laminated board and a resin plate were .~
., .
g : :
,,: ' _ ~ 3~a5~8 1 prepared in the same manner as in Example 1, except that 2,2-bis(4,4'~dicyanatophenyl)propane was used as a cyanate compound in place of XU-71787.
Example 3 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that ditrifluoro-bis(4,4'-dicyanatophenyl)methane was used as a cyanate compound in place of XU-71787.
Example 4 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that 2,2-bis(4,4'-dicyanatophenyl)propane was used as a cyanate compound in place of XU-71787, and poly-(p-; vinylbromophenylacrylate) was used as a flame retandant in place of poly-(p-vinylbromophenylmethacrylate).
Example 5 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that a mixture of 2,2-bis(4,4'-dicyanatophenyl)propane as a cyanate compound, poly-(p-vinylbromophenylmethacrylate) ., as a flame retardant ~average molecular weight: 6,600; m is about 2 and n is about 20 in the general formula (II)~ and 2,2-[4-(4-maleimidophenoxy)phenyl]propane as an aromatic bismaleimide in a ratio of 4:4:2 by weight : - 25 -~' .; :
.. ~ ,.~
1 3~5~
1 was dissolved in N,N-dimethylformamide to prepare a varnish.
Example 6 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that 2,2-bis(4,4'-diisocyanatophenyl)propane was used as an isocyanate compound in place of the cyanate compound.
Example 7 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that poly(p-vinylbromophenylacrylate [average molecular weight: 3,300; m is 2 and n is 10 in the general formula (II)] was used as a flame retardant.
Example 8 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that poly-(p-vinylbromophenylallylether) [average molecuar weight: 8,800; m i8 about 2 and n i5 about 30 in the general formula (II)] was used as a flame retardant.
Example 9 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that 2,2-bis(4,4'-diisocyanatophenyl)propane was used as an isocyanate compound in place of XU-71787 and poly(p-.
.' , .
. . ~
:. :
1 vinylbromophenylacrylate) [average molecular weight:6,600; m is about 2 and n is about 20 in the general formula (II)] was used as a flame retardant.
Example 10 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that dicyclopentanedicyanate was used as a cyanate compound in place of XU-71787.
Example 11 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that trichloropentanediisocyanate was used as an isocyanate compound in place of XU-71787.
Example 12 A laminated board and a resin plate were ,~
prepared in the same manner as in Example 1, except that a mixture composed of XU-71787 as a cyanate compound and ~'. poly~p-vinylbromophenylmethacrylate) [average molecular .
i weight: 27,000; m i9 4 and n i5 90 in the general , 20 formula ~II)] as a flame retardant in a mixing ratio of ., 7:3 by weight was used.
Comparative Example 1 ' A laminated board and a resin plate were ''i prepared in the same manner as in Example 1, except that ., .
.. ; - 27 -. ~
`' , 1 a mixture of 100 parts by weight of XU-71787 as cyanate compound and one part by weight of cobalt naphthenate was dissolved in N,N-dimethylformamide as a solvent to prepare an impregnation varnish.
Comparative Example 2 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that a polyimide material MCL-167 (trademark of a product made by Hitachi Kasei Kogyo K.K., Japan) was used in place of the resin composition Comparative Example 3 Epoxy-modified polybutadiene EP-50 (trademark of a product made by Nihon Soda K.K., Japan) and flame-retardant polytp-vinylbromophenylmethacrylate) [average molecular weight: 6,600; m is about 2 and n is about 20 in the general formula (II)] were mixed together in a mixing ratio of 20:80 by weight and dissolved in N,N'-dimethylformamide with heating at 60C for 30 minutes to prepare a varnish having a solid content of 50 % by weight.
Then, 2 parts by weight of 2,5-di(t-butyl-peroxy) hexine-3(product made by Nihon Yushi K.K., Japan) and 2 parts by weight of dicyandiamide (product made by Wako Junyaku K.K., Japan) as an epoxy curing - 25 agent were added to the thus obtained varnish on the basis of 100 parts by weight of the solid component of ., .
.
, l the varnish to prepare an impregnation varnish. With the thus prepared varnish, a laminated board and a resin plate were prepared in the same manner as in Example 1.
Comparative Example 4 ~ XU-71787 as a cyanate compound and a brominated epoxy resin Araldite 8011 (trademark of a product made by Ciba-Geigy Co., Switzerland) were mixed in a mixing ratio of 50:50 by weight and dissolved in methyliso-butylketone to prepare a varnish having a solid content 10 of 50 % by weight. One part by weight of each of cobalt naphthenate and dicyandiamide were added to the thus prepared varnish on the basis of 100 parts by weight of the solid content of the varnish to prepare an impregna-tion varnish. With the thus prepared impregnation 15 varnish, a laminated board and a resin plate were prepared in the same manner as in Example l.
Characteristics of the laminated boards and the resin plates prepared in the foregoing Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Tables 1 20 and 2, respectively.
The characteristics of the laminated boards and the resin plates were determined according to the following procedures:
3 Dielectric constant of a laminated board and a 25 resin plate was measured by an LP impedance analyzer 4192A (made by Hewlett Packard Co.) according to JIS-C-6481.
r ~ ~ - 29 -~ ., ; :
:,f!
, ~ '; , :' ' ' : ' .. . . ................ . . .
1 Bending strength of a resin plate was measured by an an autograph DDS-500 (made by Shimadzu Seisakusho K.K., Japan) by subjecting a sample, 50 mm wide x 2 mm thick x 45 mm long, to testing conditions of a span of 30 mm between two points of support at a deflection rate of 2 mm/min at room temperature and 180C.
Thermal decomposition-initiation temperature of a resin plate was measured by a high speed, differ-ential thermal balance TGD-7000RH (made by Nihon Shinku Riko K.K., Japan) by subjecting 10 mg of powdery sample to heating at a rate of 10C/min. in pure air to measure the weight loss due to the heating and determine the thermal decomposition-initiation temperature from the thus obtained weight loss-initiation temperature.
Moisture absorption of a resin plate was measured by subjecting the plate to moisture absorption in an atmosphere at 65C and 95 % relative humidity to obtain its saturation amount of moisture absorption according to JIS-C-6481.
Coefficient of thermal expansion of a laminated board was measured by a thermophysical tester TMA-1500 (made by Nihon Shinku Riko K.K., Japan) by cutting out a laminated board sample, 6 mm x 6 mm, and subjecting it to heating at a rate of 2C/min. and determining the coefficient from the thus obtained thermal expansion curve in a range of 50C to 220C.
Flame retardness of a laminated plate was evaluated by a vertical method according to UL-94 Code.
~` :
' :
, ~
"~
1 Peeling strength was measured according to JIS-C-6481 by cutting out a sample of specific size from a copper foil-lamianted board.
, . . ,:
.
.
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,,~ ~ ~ ~ o~ o . ~ ~ -,~
8 1~ ~
-- 3~ --~ 3285~8 ~ ~ O. O. In O O
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~ ~ 328528 ~ el~ O O ll~ N C
~a ~ o ~ o C: .~1 ~ ~ . N . ~1 a : , . - ,'': '' ' ~ .
-~ 328528 l Example 13 As shown in Fig. l, copper foils 4 (TST0copper foil, made by Furukawa Circuit K.K., Japan) were placed on both sides of an prepreg 3, 250 mm square, prepared from an impregnation varnish 1 and glass cloth 2 prepared in the same manner as in Example 1 and pressed between hot plates 5 of a press with heating under the same conditions as in Example 1 to cure uncured resin 1' to cured resin 7 to obtain a board 6 laminated with the copper foils 4 at both sides.
Then, the thus obtained boards 6 laminated with the copper foils 4 were subjected to resist baking, etching, drilling, etc. to form an inner layer circuit 10, as shown in Fig. 2.
Then, 11 sheets in total of an appropriate combination of the thus prepared laminated boards 8, 8' and 8'' with the circuit 10 were placed one upon another with the prepregs 3 placed therebetween and pressed between the hot plates 5 of a press with heating under the same conditions as above to form a laminated, circuit board. Then, outer layer circuits 11 and throughholes 12 were formed on the thus obtained laminated circuit board to obtain a laminated, printed ,~ circuit board 9, as shown in Fig. 9.
Cyanate compounds and isocyanate compounds having an aromatic ring in the main skeleton have a low dielectric constant and a low moisture absorption and thus can be used unexpectedly as materials for ... . .
. . ~
- `- 1 328528 l multi-layered circuit boards for electronic apparatuses such as large-scale electronic computers, etc., but require inclusion of a flame-retardant to give a satis-factory flame retardness to the materials. In the prior 5 art, a considerable decrease in the main characteristics such as the dielectric constant, moisture absorption, heat resistance, etc. is not avoidable.
The present resin composition comprising the cyanate compound or isocyanate compound and a poly(p-hydroxystyrene) derivative can satisfy the foregoingcharacteristics and a high flame retardness at the same time. The cured moldings made from the present composi-tion also have a high mechanical strength at an elevated temperature and a low coefficient of thermal expansion.
The present invention can provide multi-layered, printed circuit boards of high density, free from crack occur-rence at the preparation of multi-layered, printed circuit boards, and having an improved dimensional stability and a high reliability. When the present multi-layered, printed circuit boards are used in large-scale electronic computers, an increase in the computing speed can be expected.
;~
, , .
. - ~
- . ., .; ~ .
. ' ~
Heretofore, phenol resin, epoxy resin, polyimide resin, etc. have been used as resin materials for multi-layered printed circuit boards to be used in electronic computers, etc. Recent large-scale electronic computers require a high speed computation and thus strict characteristics are required for the multi-layered printed circuit boards for this purpose and development of new materials for the multi-layered printed circuit boards is now in progress.
Generally, the computing speed of an electronic computer largely depends on the signal transmission speed of the circuit on a multi-layered printed circuit board used in the electronic computer.
The signal transmission speed of the circuit also depends on the dielectric constant of the insulating ` layer. The lower the dielectric constant, the higher the signal transmission speed. Thus, the computing speed of an electronic computer can be improved by making a printed circuit board from materials of low 1 dielectric constant.
Polytetrafluoroethylene (PTFE), polybutadiene, -etc. are known as materials of low dielectric constant.
Furthermore, cyanate compounds (US Patent No.
4,559,3999) or isocyanate compounds (US Patent No.
4,353,7691) having a structure of low polarization based on an aromatic group or alicylic group or a combination thereof on the main chain are also known as materials of low dielectric constant.
PTFE belongs to a thermoplastic resin and has problems such as poor dimensional stability and through-hole reliability, when used in multi-layered printed circuit boards. Still furthermore, no appropriate solvent is available for PTFE and thus the lamination ; 15 bonding has been relied only on a heat fusion pressing.
Owing to a high melting temperature such as 250C to 350C, PTFE has a poor workability and problems in the handling, as compared with the conventional epoxy resin, etc.
As to the polybutadiene, on the other hand, resin materials based on a combination of 1,2-polybutadiene having double bonds on the side chains with a cross-linking type flame retardant based on bifunctional monomers have been developed [Japanese i 25 Patent Application Kokai ~Laid-open) No. 55-126~51].
When a lower molecular weight polymer is used in view of the impregnation property toward fibrous substrate materials, the tackiness of the resulting prepreg is so _ ~ _ .. . , ~ , .
. ' - , ` -l high that it is difficult to cut~ ve the prepreg and also an adverse effect is given on the lamination-bonding workability. When a higher molecular weight polymer is used in view of a low tackiness or tackfree-ness of a prepreg, the impregnation property towardfibrous substrate materials is deteriorated due to the higher varnish viscosity and it is not easy to prepare a prepreg. That is, the resulting printed circuit boards have no satisfactory qualities. Furthermore, the curing reaction is a cross-linking reaction based on radical polymerization and thus the reaction rate is so high that its control is not easy. Still furthermore, ~ polybutadiene is liable to form cracks, when molded, ; because of a high curing shrinkage and has low mechanical strength and heat resistance and a low adhesion to copper foils that form circuits.
~ he cyanate compounds or isocyanate compounds are trimerized in the presence of a catalyst to form cured products of high cross-linking density. The cured products have a low dielectric constant and good dimensional stability and heat resistance, but has no - satisfactory flame retardness as an important character-istic of printed circuit boards.
In order to improve the foregoing dis-advantages, Japanese Patent Application Kokai tLaid-open) No. 61-243844 proposes a thermosetting resin composition comprising a prepolymer of poly(p-hydroxystyrene) derivative and 1,2-polybutadiene or its ., ~B
.
,`~ . .
. ~ , 1 32~528 derivative, a laminated board using the resin composition, and a process for producing the laminated board, and Japanese Patent Application Kokai (Laid-open) NO. 62-192406 proposes a flame-retarding resin compo-~ 5 sition comprising a prepolymer of poly(p-hydroxystyrene) derivative as an essential component, and a prepreg and a laminated board using the resin composition, but the laminated boards made from these resin compositions still have problems in the moisture absorption, : 10 chronological change and mechanical characteristics at : an elevated temperature.
SUMMARY OF THE INVENTION
An object of the present invention is to ; provide a flame-retardant, thermosetting resin composition, a printed circuit board using the resin composition and a process for producing the printed circuit board, free from the foregoing disadvantages of the prior art.
According to the first aspect of the present invention, there is provided a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
. A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-~ - 4 -', ~
.
~ 1 328528 ative represented by the following general formula (II):
B - - C~2-C~ ~ B
~ ~ (II) ~ OR2 Jn wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and ! CH=CH-(X)m , m is an integer of 1 to 4 and n is an integer of 5 to 100: wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
According to the second aspect of the present invention there is provided a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - Rl - A (I) , wherein R1 is an aromatic group, an alicyclic group or ' 20 a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-., .
, - 5 -`` iD
!
, --` 1 328528 ative represented by the following general formula (II):
B - r CH2-CH r B
X)m ~ (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, Rz is selected from an alkenyl . 5 group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of 1 to 4 and n is an integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group: wherein the mixing ratio of the Compound (I) to the Compound (II) in . the resin composition is in the range of 20:80 to 80:20 by weight.
. 15 According to the third aspect of the present invention there is provided a curable material which aomprises a woven fabric or non-woven fabric of inorganic fibers or organic ~ibers, impregnated with a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
, .
~B
:
"
, .
.
. . .
.. .. . . ~ .
... . . . . .
., . ~
. .
. .
. . . . . . .
~ - . .
1 32852~
A - R1 ~ A (I) wherein R1 is selected from an aromatic group, an alicyclic group or a mixed group thereof and A is selected from a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
X)m (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an integer of 5 to lO0: wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin ; composition is in the range o~ 20:80 to 80:20 by weight;
or a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula ~
A - R1 ~ A (I) 1'~
, ~ . . . . .
.~ . : - . :
"' ~' ~ ~ ' ' . ' ' : ~ ..
- 1 32852~
- wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
, l ~ ~x)mJ (II~
: OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl : group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group: wherein the mixing ratio of the Compound ~I) to the Compound ~II) in the resin composition is in the range of 20:80 to 80:20 by weight.
According to the fourth aspect of the present invention, there is provided a printed aircuit board, which comprises a conductor of a metallic foil and an ; insulating layer made of a fibrous substrate material . - 8 -I ~S
: . -.. ~ . , impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
~ (X)m~ (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 ; to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an integer of 5 to lO0; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
According to the fifth aspect of the present , j.'~' ~, , -. , ; .
invention there is provided a printed circuit board, which comprises a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - Rl - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(X)m (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, 3 is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-~ (X)m , m is an integer of l to 4 and n is an B
'' ' ~ . ', `~ :
integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 ; 5 by weight.
According to the sixth aspect of the present invention, there is provided a multi-layered, printed circuit board, which comprises a lamination of a plurality of printed circuit boards each comprising a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) . wherein R1 is an aromatic group, an alicyclic group or amixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula : (II):
, B - - CH2-fH - B
:l ~ (X)m, (II) OR2 n wherein X is selected from a fluorine atom, a bromine ~, ', - 11 -~ .
,, .
. . , , ~ ~ ~
atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and ,CH=CH- !
(X)m , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight:
10 or printed circuit boards each comprising a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an 15 isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an ; 20 isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II) : B - - CH2-CH I B
(X~m (II) OR2 n !~
.
, .
'' -wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization S initiator residue, a polymerization-terminating agent residue, H and CH=CH-X)m , m is an integer of l to 4 and n is an integer of 5 to lO0, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
: According to the seventh aspect of the presentinvention there is provided a process for producing a printed circuit board, which comprises:
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - Rl - A ~I) wherein R~ is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
IB, :. . .. .
. . ~
~` 1 32~528 B - - CH2-~ - B
~x)m J (II) OR2 n :
wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, Rz is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent ~ residue, H and 2 CH=CH-` ~ (X)m , m is an integer of l to 4 and n is an integer of 5 to lO0, thereby forming a prepolymer;
wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight;
a step of dissolving the prepolymer in a ` solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby ; preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
According to the eighth aspect of the present :j ~
~.
.:
. . . - , ~ , .
'............ , : ~ .
: .
;. ...
` 1 328528 invention there is provided a process for producing a printed circuit board, which comprises:
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 ~ A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
, ~
B--CH2-C~I ~ B
~(X)m (II) OR2 n wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and CH=CH-(X)m , m is an integer of l to 4 and n is an Rz integer of 5 to 100 and a compound having at least one N-substituted unsaturated imido group, wherein the B
.
. . , ~ ., . . ~ ., ... , .. . . .. " .. ,. .. ` .
..
.. .. ~,, i, `. ~.
"` 1 328528 mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight, thereby forming a prepolymer;
a step of dissolving the prepolymer in a solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby - preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
The present inventors have found that a resin composition having a good flame retardness, a low moisture absorption and a high mechanical strength at an elevated temperature can be obtained without impairing the dielectric constant by combining at least one of cyanate compounds and isocyanate compounds represented by the foregoing general formula (I) with a cross-linking type, flame retardant represented general formula (II) and have established the present invention.
In the present invention, the aromatic group and the alicyclic group represent by Rl in the general formula (I) include:
( C ) m ( C ) ~( ~
etc.
' ' j ~
, .
-- 1 wherein C is -H, -CH3, -CH2CH3; D is -OCN and -NCO;
Il l l 11 E is -, -CH2-, -O-, -S-, -C- , -C- , -f- or -S- ;
: m is an integer of 1 to 4 and n is O and an integer of 1 ~: to 3, and the mixed group thereof is a group having at least a few of the foregoing aromatic and alicyclic groups in the skeleton structure and can have a plurality of the same aromatic or alicyclic groups as linked in succession in the skeleton structure.
Specific examples of the compounds represented by the general formula (I) include 2,2-bis(4,4'-di-cyanatophenyl)propane, 2,2-bis(4,4'-diisocyanatophenyl)-propane, tetramethylxylenedicyanate, tetramethylxylene-diisocyanate, diphenylmethane dicyanate, diphenyl-methanediisocyanate, cyanates and isocyanates whose R1 is 4,4'-dihydroxydiphenyloxide, resorcinol, 4,4'-thio-diphenol, 3,3',5,5'-tetrabromobisphenol-A, 2,2',6,~'-tetrabromobisphenol-A, 3-phenylbisphenol-A, 4,4'-di-hydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,2',4,4'-: tetrahydroxybiphenylmethane, 2,2',6,6'-tetramethyl-3,3',5,5'-tetrabromobisphenol-A, 5,5'-dimethoxybis-phenol-A, bisphenol of dicyclopentadiene, or bisphenol of tricyclopentadiene, polycyanates and polyisocyanates of phenol-formaldehyde condensates, polycyanates and polyisocyanates of phenoldicyclopentadiene condensates, polycyanates and polyisocyanates of 2,2',4,4'-tetra-hydroxy diphenylmethane, etc. and can be used alone or .~
.~
:-.
- 1 32~528 1 in combination of at least two thereof.
Specific examples of the compound represented by the general formula (II) include poly(p-vinylbromo-phenylallylether), poly (p-vinyl-bromophenylisopropenyl-ether), poly(p-vinylbromophenyl-l,l'-dimethylbutenyl-ether), poly(p-vinylbromophenylmethacrylate), poly(p-inylbromophenylallylether), etc, where n of the compound (II) can be an integer of 5 to 100, and depends on the species and molecular weight of the compound ~I) to be used together and also on a mixing ratio of the compound ~I) to the compound ~II). When n exceeds 100, the viscosity of the resin composition will be higher and the impregnation toward the substrate material will be deteriorated, resulting in occurrence of voids at the lamination-bonding. When n is below 5, on the other hand, the preservation stability of the resin composi-tion will be deteriorated and the flowability of the resin composition will be higher, resulting in the resin loss at the lamination-bonding.
The mixing ratio of the compound (I) to the compound ~II) in the resin composition is in a range of 20:80 to 80:20 by weight. When the compound (I) is contained in a mixing ratio of more than 80, no satisfactory flame retardness can be obtained, whereas the mixing ratio of the compound (II) is more than 80, the feature of materials of low dielectric constant cannot be fully obtained.
A compound having at least one of N-;, .. . .
1 substituted, unsaturated imido groups can be added to the resin composition comprising the compound (I) and the compound (II) as a cross-linking promoter, and in-cludes, for example, bismaleimides such as N-substituted phenylmaleimide, phenylcitraconimide, phenylitacon-imide, phenylnadic imide (phenylmethylendomethylene-tetrahydrophthalimide), N,N'-p-phenylenebismaleimide, N,N'-p-phenylenebismethylendomethylenetetraphthalimide, N,N'-p-phenylenebiscitraconimide, N,N'-p-phenylenebis-itaconimide, N,N'-m-xylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-(methylene-di-p-phenylene)bismaleimide, N,N'-4,4'-diphenylthioetherbismaleimide, N,N'-4,4'-diphenylether-bismaleimide, N,N'-methylenebis(3-chloro-p-phenylene)-bismaleimide, N,N'-(sulfonyl-di-p-phenylene)bismale-imide, N,N'-4,4'-diphenylcyclohexanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis~4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimido-2-trifluoromethylphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, etc., and multi-valent maleimides obtained by reaction of a condensate of aniline and aldehyde with maleic anhydride and repre-sented by the following general formula (III), etc:
CH2- ~ CH2- ~ (III) ~N~ ~N~ ,N\
of clo of clo of clo CH = CH ~ CH = CH , P CH = CH
' -- .
.
:'' ' , ' ', i, -: .
1 32852~
1 where p is an integer of 1 to 10.
The present process for producing a laminated board will be described below.
A resin composition composed of the compound (I) and the compound (II) is dissolved in an organic solvent in a mixing ratio in the aforementioned range to prepare a varnish having a resin content of 20 to 80% by weight. To promote the dissolution, heating can be conducted. As the organic solvent, toluene, xylene, methylethylketone, methylisobutylketone, methanol, ethanol, 3-methoxypropanol, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trichloroethylene, etc., or those which can uniformly dissolve the compounds (I) and (II) can be used alone or in combination.
A trimerization catalyst for the cyanate group or the isocyanate group and a radical polymerization initiator is then added to the thus prepared varnish to make an impregnation varnish. As the trimerization catalyst, metal salts such as cobalt naphthenate, cobalt octenoate, zinc octenoate, potassium acetate, sodium acetate, sodium cyanide, sodium cyanate, sodium ; isocyanate, sodium boride, etc.; sodium methoxide;
sodium hydroxide; organic base such as pyridin; tertiary amines such as triethylamine, etc.; Lewis acids such as aluminum chloride, bromine trifluoride, ferric chloride, titanium chloride, zinc chloride, etc. can be used. As ' the radical polymerization initiator, benzoyl peroxide, :, ',"
..
1 dicumyl peroxide, methylethylketone peroxide, t-butyl peroxylaurate, di-t-butyl peroxyphthalate, dibenzyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, etc. can be used. 0.1 to 10 parts by weight of these trimerization catalyst and radical polymerization initiator is used per 100 parts by weight of the resin composition.
Then, a fibrous substrate material is impreg-nated and coated with the thus prepared impregnation varnish and dried at room temperature to 170C to obtain a prepreg free from the tackiness. The drying tempera-ture depends on the species of the solvent and radical polymerization initiator used.
Then, a desired number of the thus obtained prepregs is laid upon one another and cured with heating at 120C to 250C under a pressure of 1 to 100 kg f/cm2 to obtain a laminated board.
As the fibrous substrate material, those usually used as laminated board materials can be used in the present invention. Woven fabrics or non-woven fabrics of inorganic fibrous substrate materials such as glass fibers, for example, E glass fibers, C glass fibers, A glass fibers, S glass fibers, D glass fibers, YM-31-A glass fibers containing SiO2, A12O3, etc. as main components, and A glass fibers made of ~uartz, etc.
or woven fabrics or non-woven fabrics of organic fibers such as aramid fibers containing polymer compounds having as aromatic polyamide-imide skeleton can be used ;
- : . . . ' ~` 1 328528 1 in the present invention.
In the present invention, an inorganic filler such as silica powder, etc. or an organic filler such as perfluoroethylene powder, polyimide powder, polyamide powder, etc. can be added to the resin composition, and it is particularly important in attaining the effect of the present invention to use a filler having a di-electric constant of not more than 3.3.
That the present thermosetting resin composi-tion can produce a laminated board of low dielectricconstant and a good flame retardness is not only due to the fact that the cyanate compound or the isocyanate compound (I) itself has a low dielectric constant, but also due to the fact that the cross-linking type, polymeric flame retardant (II) is a material of un-expectedly low dielectric constant and further that the flame retardness and electric characteristics are not deteriorated even by copolymerization of the cross-linking type, polymeric flame retardant ~II) with the cyanate or isocyanate compound (I).
The present invention will be described in detail below, referring to Examples and the accompanying drawin~s.
q BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows process steps for preparing a board laminated with copper foils at both outer sides, as viewed in cross-section.
' ~;' . ~
. .......................................... . .
-`- 1 328528 l Fig. 2 shows a process step for preparing an inner layer circuit board as viewed in cross-section.
Fig. 3 shows a process step for preparing a multi-layered printed circuit board.
In Figs. 1 to 3, numerals 1 is a varnish prepared from the present resin composition; 1' is uncured resin; 2 a glass cloth; 3 a prepreg; 4 a copper foil; 5 a hot plate; 6 a copper-laminated board; 7_a cured resin; 8,8' and 8" inner layer circuit boards; 9 a multi-layered, printed circuit board; 10 an inner layer printed circuit; 11 an outer layer printed circuit; and l2 a through hole.
PREFERRED EMBODIMENTS OF THE INVENTION
Example 1 XU-71787 (trademark of a cyanate compound prepared by Dow Chemical Company, USA) represented by the general formula (I; and poly-(p-vinylbromophenyl-methacrylate represented by the general formula ~II) [average molecular weight: 6,600; m is about 2 and n is about 20 in the general formula (II)] as a flame retard-ant were mixed in a mixing ratio of 1:1 by weight and the resulting resin compositlon was dissolved in N,N-dimethylformamide as a solvent with heating at 60C for 30 minutes to prepare a varnish having a solid content of 50 % by weight. After cooling, 0.5 parts by weight of 2,5-di(t-butylperoxy) hexine-3(made by Nihon Yushi K.K., Japan) as a radical polymerization initiator and ., .
. ~ . . .
. , ~ :
,, . : .
1 ~28528 1 0.5 parts by weight of cobalt naphthenate as a tri-merization catalyst for the cyanate compound were added to the varnish on the basis of 100 parts by weight of the resin composition to prepare an impregnation s varnish.
Glass cloth (250 mm square; thickness: 0.05 mm; E glass made by Nitto Boseki K.K., Japan) was impregnated and coated with the thus prepared varnish and dried in air at 150C for 10 minutes to prepare a prepreg, 250 mm square, (resin content: 40 - 70 % by weight).
Then, 20 sheets of the thus prepared prepregs were laid one upon another and pressed between a pair of hot plats under a pressure of 30 kg f/cm2 at first at 130C for 40 minuts, then at 170C for one hour, and lastly at 200C for one hour with heating to cure the resin to obtain a laminated board.
Separately, the impregnation varnish was applied to a polyethylene terephthalate sheet and dried at 150C for 10 minutes to obtain a powdery resin ~ composition. The thus obtained resin composition was ;~ press-molded into a plate form, 15 cm x 10 cm x 2 mm thick, and cured under the same conditions as used for the preparation of the prepreg as above, to form a resin plate.
:.
Example 2 A laminated board and a resin plate were .~
., .
g : :
,,: ' _ ~ 3~a5~8 1 prepared in the same manner as in Example 1, except that 2,2-bis(4,4'~dicyanatophenyl)propane was used as a cyanate compound in place of XU-71787.
Example 3 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that ditrifluoro-bis(4,4'-dicyanatophenyl)methane was used as a cyanate compound in place of XU-71787.
Example 4 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that 2,2-bis(4,4'-dicyanatophenyl)propane was used as a cyanate compound in place of XU-71787, and poly-(p-; vinylbromophenylacrylate) was used as a flame retandant in place of poly-(p-vinylbromophenylmethacrylate).
Example 5 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that a mixture of 2,2-bis(4,4'-dicyanatophenyl)propane as a cyanate compound, poly-(p-vinylbromophenylmethacrylate) ., as a flame retardant ~average molecular weight: 6,600; m is about 2 and n is about 20 in the general formula (II)~ and 2,2-[4-(4-maleimidophenoxy)phenyl]propane as an aromatic bismaleimide in a ratio of 4:4:2 by weight : - 25 -~' .; :
.. ~ ,.~
1 3~5~
1 was dissolved in N,N-dimethylformamide to prepare a varnish.
Example 6 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that 2,2-bis(4,4'-diisocyanatophenyl)propane was used as an isocyanate compound in place of the cyanate compound.
Example 7 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that poly(p-vinylbromophenylacrylate [average molecular weight: 3,300; m is 2 and n is 10 in the general formula (II)] was used as a flame retardant.
Example 8 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that poly-(p-vinylbromophenylallylether) [average molecuar weight: 8,800; m i8 about 2 and n i5 about 30 in the general formula (II)] was used as a flame retardant.
Example 9 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that 2,2-bis(4,4'-diisocyanatophenyl)propane was used as an isocyanate compound in place of XU-71787 and poly(p-.
.' , .
. . ~
:. :
1 vinylbromophenylacrylate) [average molecular weight:6,600; m is about 2 and n is about 20 in the general formula (II)] was used as a flame retardant.
Example 10 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that dicyclopentanedicyanate was used as a cyanate compound in place of XU-71787.
Example 11 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that trichloropentanediisocyanate was used as an isocyanate compound in place of XU-71787.
Example 12 A laminated board and a resin plate were ,~
prepared in the same manner as in Example 1, except that a mixture composed of XU-71787 as a cyanate compound and ~'. poly~p-vinylbromophenylmethacrylate) [average molecular .
i weight: 27,000; m i9 4 and n i5 90 in the general , 20 formula ~II)] as a flame retardant in a mixing ratio of ., 7:3 by weight was used.
Comparative Example 1 ' A laminated board and a resin plate were ''i prepared in the same manner as in Example 1, except that ., .
.. ; - 27 -. ~
`' , 1 a mixture of 100 parts by weight of XU-71787 as cyanate compound and one part by weight of cobalt naphthenate was dissolved in N,N-dimethylformamide as a solvent to prepare an impregnation varnish.
Comparative Example 2 A laminated board and a resin plate were prepared in the same manner as in Example 1, except that a polyimide material MCL-167 (trademark of a product made by Hitachi Kasei Kogyo K.K., Japan) was used in place of the resin composition Comparative Example 3 Epoxy-modified polybutadiene EP-50 (trademark of a product made by Nihon Soda K.K., Japan) and flame-retardant polytp-vinylbromophenylmethacrylate) [average molecular weight: 6,600; m is about 2 and n is about 20 in the general formula (II)] were mixed together in a mixing ratio of 20:80 by weight and dissolved in N,N'-dimethylformamide with heating at 60C for 30 minutes to prepare a varnish having a solid content of 50 % by weight.
Then, 2 parts by weight of 2,5-di(t-butyl-peroxy) hexine-3(product made by Nihon Yushi K.K., Japan) and 2 parts by weight of dicyandiamide (product made by Wako Junyaku K.K., Japan) as an epoxy curing - 25 agent were added to the thus obtained varnish on the basis of 100 parts by weight of the solid component of ., .
.
, l the varnish to prepare an impregnation varnish. With the thus prepared varnish, a laminated board and a resin plate were prepared in the same manner as in Example 1.
Comparative Example 4 ~ XU-71787 as a cyanate compound and a brominated epoxy resin Araldite 8011 (trademark of a product made by Ciba-Geigy Co., Switzerland) were mixed in a mixing ratio of 50:50 by weight and dissolved in methyliso-butylketone to prepare a varnish having a solid content 10 of 50 % by weight. One part by weight of each of cobalt naphthenate and dicyandiamide were added to the thus prepared varnish on the basis of 100 parts by weight of the solid content of the varnish to prepare an impregna-tion varnish. With the thus prepared impregnation 15 varnish, a laminated board and a resin plate were prepared in the same manner as in Example l.
Characteristics of the laminated boards and the resin plates prepared in the foregoing Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Tables 1 20 and 2, respectively.
The characteristics of the laminated boards and the resin plates were determined according to the following procedures:
3 Dielectric constant of a laminated board and a 25 resin plate was measured by an LP impedance analyzer 4192A (made by Hewlett Packard Co.) according to JIS-C-6481.
r ~ ~ - 29 -~ ., ; :
:,f!
, ~ '; , :' ' ' : ' .. . . ................ . . .
1 Bending strength of a resin plate was measured by an an autograph DDS-500 (made by Shimadzu Seisakusho K.K., Japan) by subjecting a sample, 50 mm wide x 2 mm thick x 45 mm long, to testing conditions of a span of 30 mm between two points of support at a deflection rate of 2 mm/min at room temperature and 180C.
Thermal decomposition-initiation temperature of a resin plate was measured by a high speed, differ-ential thermal balance TGD-7000RH (made by Nihon Shinku Riko K.K., Japan) by subjecting 10 mg of powdery sample to heating at a rate of 10C/min. in pure air to measure the weight loss due to the heating and determine the thermal decomposition-initiation temperature from the thus obtained weight loss-initiation temperature.
Moisture absorption of a resin plate was measured by subjecting the plate to moisture absorption in an atmosphere at 65C and 95 % relative humidity to obtain its saturation amount of moisture absorption according to JIS-C-6481.
Coefficient of thermal expansion of a laminated board was measured by a thermophysical tester TMA-1500 (made by Nihon Shinku Riko K.K., Japan) by cutting out a laminated board sample, 6 mm x 6 mm, and subjecting it to heating at a rate of 2C/min. and determining the coefficient from the thus obtained thermal expansion curve in a range of 50C to 220C.
Flame retardness of a laminated plate was evaluated by a vertical method according to UL-94 Code.
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1 Peeling strength was measured according to JIS-C-6481 by cutting out a sample of specific size from a copper foil-lamianted board.
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-~ 328528 l Example 13 As shown in Fig. l, copper foils 4 (TST0copper foil, made by Furukawa Circuit K.K., Japan) were placed on both sides of an prepreg 3, 250 mm square, prepared from an impregnation varnish 1 and glass cloth 2 prepared in the same manner as in Example 1 and pressed between hot plates 5 of a press with heating under the same conditions as in Example 1 to cure uncured resin 1' to cured resin 7 to obtain a board 6 laminated with the copper foils 4 at both sides.
Then, the thus obtained boards 6 laminated with the copper foils 4 were subjected to resist baking, etching, drilling, etc. to form an inner layer circuit 10, as shown in Fig. 2.
Then, 11 sheets in total of an appropriate combination of the thus prepared laminated boards 8, 8' and 8'' with the circuit 10 were placed one upon another with the prepregs 3 placed therebetween and pressed between the hot plates 5 of a press with heating under the same conditions as above to form a laminated, circuit board. Then, outer layer circuits 11 and throughholes 12 were formed on the thus obtained laminated circuit board to obtain a laminated, printed ,~ circuit board 9, as shown in Fig. 9.
Cyanate compounds and isocyanate compounds having an aromatic ring in the main skeleton have a low dielectric constant and a low moisture absorption and thus can be used unexpectedly as materials for ... . .
. . ~
- `- 1 328528 l multi-layered circuit boards for electronic apparatuses such as large-scale electronic computers, etc., but require inclusion of a flame-retardant to give a satis-factory flame retardness to the materials. In the prior 5 art, a considerable decrease in the main characteristics such as the dielectric constant, moisture absorption, heat resistance, etc. is not avoidable.
The present resin composition comprising the cyanate compound or isocyanate compound and a poly(p-hydroxystyrene) derivative can satisfy the foregoingcharacteristics and a high flame retardness at the same time. The cured moldings made from the present composi-tion also have a high mechanical strength at an elevated temperature and a low coefficient of thermal expansion.
The present invention can provide multi-layered, printed circuit boards of high density, free from crack occur-rence at the preparation of multi-layered, printed circuit boards, and having an improved dimensional stability and a high reliability. When the present multi-layered, printed circuit boards are used in large-scale electronic computers, an increase in the computing speed can be expected.
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Claims (8)
1. A thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and (X)m , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and (X)m , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
2. A thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
3. A curable material which comprises a woven fabric or non-woven fabric of inorganic fibers or organic fibers, impregnated with a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is selected from an aromatic group, an alicyclic group or a mixed group thereof and A is selected from a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100: wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight;
or a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
A - R1 - A (I) wherein R1 is selected from an aromatic group, an alicyclic group or a mixed group thereof and A is selected from a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100: wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight;
or a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
4. A printed circuit board, which comprises a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
5. A printed circuit board, which comprises a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriva-tive represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
6. A multi-layered, printed circuit board, which comprises a lamination of a plurality of printed circuit boards each comprising a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight, or printed circuit boards each comprising a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight, or printed circuit boards each comprising a conductor of a metallic foil and an insulating layer made of a fibrous substrate material impregnated and cured with a thermosetting resin composition, the thermosetting resin composition comprising a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) derivative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, and a compound having at least one N-substituted unsaturated imido group; wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight.
7. A process for producing a printed circuit board, which comprises:
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, thereby forming a prepolymer;
wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight;
a step of dissolving the prepolymer in a solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100, thereby forming a prepolymer;
wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight;
a step of dissolving the prepolymer in a solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
8. A process for producing a printed circuit board, which comprises:
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100 and a compound having at least one N-substituted unsaturated imido group, wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight, thereby forming a prepolymer;
a step of dissolving the prepolymer in a solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
a step of heating a thermosetting resin composition which comprises a cyanate compound or an isocyanate compound represented by the following general formula (I):
A - R1 - A (I) wherein R1 is an aromatic group, an alicyclic group or a mixed group thereof and A is a cyanate group or an isocyanate group, and a poly-(p-hydroxystyrene) deriv-ative represented by the following general formula (II):
(II) wherein X is selected from a fluorine atom, a bromine atom and a chlorine atom, R2 is selected from an alkenyl group and an unsaturated carboxyl group, each having 2 to 4 carbon atoms, B is selected from a polymerization initiator residue, a polymerization-terminating agent residue, H and , m is an integer of 1 to 4 and n is an integer of 5 to 100 and a compound having at least one N-substituted unsaturated imido group, wherein the mixing ratio of the Compound (I) to the Compound (II) in the resin composition is in the range of 20:80 to 80:20 by weight, thereby forming a prepolymer;
a step of dissolving the prepolymer in a solvent, thereby forming an impregnation varnish, impregnating a fibrous substrate material with the impregnation varnish, followed by drying, thereby preparing a prepreg; and a step of laminating a plurality of the thus obtained prepregs, thereby obtaining a laminate, and pressing the laminate together with conductor metal foils with heating.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63-246978 | 1988-09-30 | ||
JP24697888 | 1988-09-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1328528C true CA1328528C (en) | 1994-04-12 |
Family
ID=17156547
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000614073A Expired - Fee Related CA1328528C (en) | 1988-09-30 | 1989-09-28 | Thermosetting resin composition, printed circuit board using the resin composition and process for producing printed circuit board |
Country Status (5)
Country | Link |
---|---|
US (1) | US5045381A (en) |
EP (1) | EP0364785B1 (en) |
KR (1) | KR0155542B1 (en) |
CA (1) | CA1328528C (en) |
DE (1) | DE68921407T2 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5045381A (en) * | 1988-09-30 | 1991-09-03 | Hitachi, Ltd. | Thermosetting resin composition, printed circuit board using the resin composition and process for producing printed circuit board |
JPH07120858B2 (en) * | 1990-03-30 | 1995-12-20 | 株式会社日立製作所 | Multilayer printed circuit board and manufacturing method thereof |
TW210422B (en) * | 1991-06-04 | 1993-08-01 | Akzo Nv | |
US5360887A (en) * | 1992-07-29 | 1994-11-01 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Flame-retarded thermosetting resin composition, prepregs and electrical laminates made therefrom |
US5688601A (en) * | 1994-03-25 | 1997-11-18 | Caschem, Inc. | Exterior protective layer for an electrical component |
TW398163B (en) * | 1996-10-09 | 2000-07-11 | Matsushita Electric Ind Co Ltd | The plate for heat transfer substrate and manufacturing method thereof, the heat-transfer substrate using such plate and manufacturing method thereof |
US6083340A (en) * | 1997-02-28 | 2000-07-04 | Hokuriku Electric Industry Co., Ltd. | Process for manufacturing a multi-layer circuit board |
US6038133A (en) * | 1997-11-25 | 2000-03-14 | Matsushita Electric Industrial Co., Ltd. | Circuit component built-in module and method for producing the same |
JP3760771B2 (en) * | 2001-01-16 | 2006-03-29 | 松下電器産業株式会社 | Circuit forming substrate and method of manufacturing circuit forming substrate |
US7315000B2 (en) * | 2003-07-27 | 2008-01-01 | Sandisk Il Ltd. | Electronic module with dual connectivity |
JP2015509113A (en) * | 2011-12-12 | 2015-03-26 | エルジー・ケム・リミテッド | Cyanate ester resin composition for circuit board production and flexible metal foil laminate including the same |
US9668345B2 (en) * | 2012-03-30 | 2017-05-30 | Hitachi Chemical Company, Ltd. | Multilayer wiring board with metal foil wiring layer, wire wiring layer, and interlayer conduction hole |
WO2018088493A1 (en) * | 2016-11-09 | 2018-05-17 | 日立化成株式会社 | Printed wiring board and semiconductor package |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1220132B (en) * | 1964-04-10 | 1966-06-30 | Bayer Ag | Process for the production of nitrogen-containing polyadducts |
US4578439A (en) * | 1984-08-09 | 1986-03-25 | The Dow Chemical Company | Styryl pyridine cyanates, styryl pyrazine cyanates and polymers thereof |
JPS61243844A (en) * | 1985-04-23 | 1986-10-30 | Hitachi Ltd | Thermosetting resin composition, laminated sheet and production thereof |
JPS62161847A (en) * | 1986-01-10 | 1987-07-17 | Hitachi Ltd | Thermosetting resin composition, laminate using same and production thereof |
US4774634A (en) * | 1986-01-21 | 1988-09-27 | Key Tronic Corporation | Printed circuit board assembly |
DE3750641T2 (en) * | 1986-02-19 | 1995-04-06 | Hitachi Ltd | Thermosetting resin, prepreg and use in laminates. |
EP0290860B1 (en) * | 1987-04-27 | 1995-01-25 | Mitsubishi Gas Chemical Company, Inc. | Thermosetting resin composition |
JPS63281152A (en) * | 1987-05-14 | 1988-11-17 | Hitachi Chem Co Ltd | Photosensitive resin composition |
JPS64145A (en) * | 1987-06-22 | 1989-01-05 | Hitachi Ltd | Thermosetting resin composition, prepreg and laminate |
US5045381A (en) * | 1988-09-30 | 1991-09-03 | Hitachi, Ltd. | Thermosetting resin composition, printed circuit board using the resin composition and process for producing printed circuit board |
-
1989
- 1989-09-27 US US07/413,070 patent/US5045381A/en not_active Expired - Fee Related
- 1989-09-28 CA CA000614073A patent/CA1328528C/en not_active Expired - Fee Related
- 1989-09-29 DE DE68921407T patent/DE68921407T2/en not_active Expired - Fee Related
- 1989-09-29 KR KR1019890014044A patent/KR0155542B1/en not_active IP Right Cessation
- 1989-09-29 EP EP89118041A patent/EP0364785B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0364785B1 (en) | 1995-03-01 |
KR0155542B1 (en) | 1998-12-01 |
DE68921407T2 (en) | 1995-07-06 |
DE68921407D1 (en) | 1995-04-06 |
US5045381A (en) | 1991-09-03 |
KR900004865A (en) | 1990-04-13 |
EP0364785A1 (en) | 1990-04-25 |
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